TW419686B - Dielectric ceramic, method for producing the same, laminated ceramic electronic element, and method for producing the same - Google Patents

Abstract

The present invention provides a dielectric ceramic which exhibits an excellent electrostatic capacity-temperature characteristic; which allows use of a base metal such as nickel; which can be fired in a reducing atmosphere; and which is suitable for constituting a dielectric ceramic layer of a laminated ceramic electronic element such as a laminated ceramic capacitor. The dielectric ceramic is obtained by firing barium titanate powder in which a caxis/a-axis ratio in the perovskite structure is in the range of 1.003 to 1.010 and an amount of OH groups in the crystal lattice is 1 wt.% or less. The barium titanate powder serving as a starting material preferably has a maximum particle size of 0.5 mu m or less and an average particle size of 0.1-0.3 mu m, and individual particles of the barium titanate powder comprise a low-crystallinity portion 21 and a high-crystallinity portion 23, with the diameter of the low-crystallinity portion being less than 0.65 times the particle size of the powder. Moreover, when sintered, the powder satisfies the ratio of (average grain size of the fired dielectric ceramic)/(average particle size of barium titanate powder serving as a starting material), which is referred to as R, of 0.90-1.2, to thereby suppress considerable grain growth. The invention also discloses a laminated ceramic electronic element including a laminate of a plurality of layers of the above-mentioned dielectric ceramic, as well as a method for producing the same.

Description

4ί ^ 686 λ; ----- Β7 _________ V. Description of the invention (t) Background of the invention The scope of the present invention is related to a dielectric ceramic, which is advantageous for use on a laminated ceramic daughter element, such as having A multilayer ceramic capacitor with an inner conductor formed from a base metal such as a wire or a nickel alloy, and a method for manufacturing VI ceramics. The invention also relates to a kind of multilayer ceramic formed by dielectric ceramics, ... to pass electronic components, and a method for manufacturing the same. Relevant technical description Miniaturization and price reduction of multilayer ceramic electronic components are continuously ongoing. For example. In such a ceramic electronic component, the ceramic layer has been thinned, and the base metal has also been made into one or two conductors. In multilayer ceramic capacitors (a type of multilayer ceramic electronic components), a dielectric ceramic layer has been made as thin as about 3 microns, and a base metal like * Cu4Ni— has also been used as an internal conductor. (Ie internal electrode) material 3 However, when the ceramic layer becomes thinner, the electric field strength applied to the layer will increase, which results in the use of a dielectric material as the ceramic layer (which shows a large change in dielectric constant due to electric field induction) )The problem. Reducing the size of ceramic grains in the thickness direction of the ceramic layer also causes reliability problems. In order to overcome this situation, the central government bureau of the Ministry of Economic Affairs' employee consumer cooperatives printed this patent application and publication No. 9_241074, No. 9-24 丨 075, etc. have been proposed, by increasing the ceramics in the direction of the thickness of the dielectric ceramic layer The grain size can improve the reliability of ceramic materials. Therefore, controlling the size of ceramic grains can reduce the change in dielectric constant due to electric field or temperature induction. However, in the above-mentioned conventional technology, when the thickness of the dielectric ceramic layer is about t -4-this paper size Applicable to China National Standard i CNS > A4 specification (210 × 297 mm) Consumer Co-operation of the Central Bureau of Standards of the Ministry of Economic Affairs Du Yinzhi 9866 A7 ---_______________ V. Description of the invention (2) When the micron or lower is maintained Reliability, but the change in temperature-dielectric constant characteristics increases. Therefore, it is difficult to obtain stable temperature-dielectric constant characteristics with high reproducibility. In order to ensure a stable temperature-dielectric constant characteristic, the electric field strength must be reduced, and the rated voltage of the sub-elements produced must also be reduced. Therefore, it is difficult or impossible to achieve a thin layer as thin as 1 micron or less if the conventional techniques are used to solve the problem. SUMMARY OF THE INVENTION According to the foregoing, the present invention indicates a dielectric ceramic that is beneficial for use in a multilayer ceramic electronic component. The multilayer ceramic electronic component includes a thin ceramic layer with a thickness of 1 micron and a thickness of 4 microns, and a manufacturing method. The dielectric ceramic method. The invention also indicates a multilayer ceramic electronic component composed of a dielectric ceramic and a method for manufacturing the same. In one aspect of the invention, there is provided a dielectric ceramic, which is obtained by sintering barium titanate powder with a perovskite structure. The perovskite structure has a £ _axis / 3_ pumping ratio of 丨 003 Within the range of 10 to 10, and the content of radicals in the crystal lattice is 1.0% by weight or less. In another aspect of the present invention, a method of manufacturing a dielectric ceramic is provided. The method includes the step of providing the above barium titanate powder, wherein the c-pump / a-axis ratio in the perovskite structure is from 1.003 to 1 '. 〇 [〇 within the range of the garden, and the lattice order contained 疋 0 Η group is 1.0% by weight or less: and the step of sintered barium titanate powder 3 〇Η group content is determined in 丨At 50t or higher, the amount lost during the thermogravimetric analysis of the sample 3 -5- National Pioneer (CNS) Λ4 Specification (157x297 cm) ------ ^^- -----, π ------ A, (Please read the precautions on the back before filling in this page) A7 B7 4J9686 V. Description of the invention (3) The maximum titanate lock powder particle size is preferably no more than 〇 5 microns, and the average particle size is 0.1 to 0.3 microns. In addition, the above-mentioned L particles preferably contain-low crystallinity Shao and-high crystallinity Shao, and the diameter of the low crystallinity part is preferably low It is 0 to 65 times the particle size of the powder. As shown in Fig. 2 (transmission electron micrograph of barium acetic acid powder) and Fig. 3 (illustrative drawing of the previous figure), The term "low crystallinity portion" 21 represents a region containing lattice defects such as voids 22, and the term "high crystallinity portion" 23 as used herein means a region that does not include such lattice defects. In addition, when the ratio of (average grain size of the dielectric ceramics after being burnt) / (average particle size of the acid-locking powder provided) is represented, please be in the range of 0-90 to 1.2. The crystal grains constituting the dielectric ceramic of the present invention may have a core-shell structure with a core and a shell composition and a crystal system different from each other, 4 may have a homogeneous structure, which has a uniform composition and a crystal system structure. The term used herein " "Crystalline system" refers to the crystal system of a perovskite crystal, that is, a cubic crystal system, with a perovskite structure in which the ^ axis is _ axis ratio of 1, or refers to a tetragonal system, It has a c __ / a-axis ratio of 1 or more in the chitin structure. In yet another aspect of the present invention, a multilayer ceramic electronic component is provided, including a multilayer composed of a plurality of ceramic layers, and Adjacent to the formation of a specific interface between dielectric ceramic layers More specifically, in the present invention, the dielectric ceramic layer included in the laminated ceramic electronic component is composed of a dielectric ceramic, and this dielectric ceramic is a -6-size paper that applies the Chinese national standard (CNS) A4 specification (210X29 * 7mm) u. IIJ I- 11-- — ^ ― i ^ imn ^ i I .. 1 ^ 1-「1 ^^ 1 ϋ n _ n 1 ^ 1 ', T (Please read the precautions on the back before &/; this page) A7 B7 4 ^ 686 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (4) Barium titanate powder with perovskite structure 结构Obtained by firing, the C-axis / a-axis ratio in this perovskite structure is in the range of 003 to 1010, and the content of radicals in the crystal lattice is 1.0% by weight or less. In the multilayer ceramic electronic component described above, the 'internal conductor' preferably contains a base metal such as nickel or a nickel alloy. The multilayer ceramic electronic component may further include a plurality of external electrodes at positions on different sides. In this example, the inner conductor is formed so that one end of each inner 4 conductor is exposed in the side for electrical connection to one of the outer 4 poles. Such a structure is typically applied to a multilayer ceramic capacitor. In a further aspect of the present invention, it provides a method for manufacturing a multilayer ceramic electronic component. The method includes a step of feeding a barium titanate powder, wherein Jochin The c-axis / a-axis ratio in the ore structure is within the range of 1.03 to 1.00 'and the content of 0H in the crystal lattice is 10% by weight or less; making a laminate' The multilayer contains barium titanate powder and several ceramic green sheets and internal electrodes, so those internal electrodes appear along the special interface of the ceramic green sheet: and the calcined barium titanate powder is This provides a dielectric ceramic. The brief description of the drawings is better understood by considering the associated drawings and referring to the detailed insertions of the following preferred embodiments. The various other purposes, Tetons, and accompanying advantages of the present invention will be immediately recognized correctly. The drawings are as follows: FIG. 1 is a cross-sectional view of a specific embodiment of the present invention, showing a layered ceramic capacitor 1; FIG. 2 is a barium titanate paper provided for manufacturing a dielectric ceramic according to the present invention; The scale is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 0X 297 mm) 1iI-^ ——-—— t .—— (Please read the notes on the back before filling this page) Standard 419686 A7 B7 printed by quasi-station employee consumer cooperatives V. Description of the invention (5) " " ^ Transmission electron microscope photograph of powder; and Figure 3 is an explanatory formula of the electron microscope photograph shown in Figure 2 Draw a picture. Description of the preferred embodiment The chemical formula of the composition of the barium titanate powder used in the present invention is: (Bai.xXJn ^ TihUO3. Its composition is not further restricted exactly. X may include Ca, a single rare earth element, and A combination of two or more of them. Y may include a single species such as Zr or Mn, and a combination of two or more of them. Generally, T′m is preferably from 100 to 035, end-view titanium The composition of the acid-frequency powder is determined to obtain a non-returnable dielectric ceramic finish. The barium titanate powder which is advantageous for use has a perovskite structure, and the ratio of c_axis / a_axis is in the range of 1.003 to 1.01. Circle 10. Furthermore, the content of OH groups in the crystal lattice is 1.0% by weight or less; the largest particle size is not more than 0.05 micrometers; and the average grain size is 0.1 to 0.3 micrometers. Such titanium The barium acid powder can be obtained by heat-treating a jump pin powder, which is made by a wet synthesis method such as a hydrothermal synthesis method, a hydrolysis method, or a sol-gel method. To synthesize, Solid-phase method The stearic acid 'oxides of the elements of the powder are mixed and heat-treated. In the above-mentioned heat treatment, the conditions for moderate grain growth are selected to achieve a c_axis / a-pump ratio of south to 1.003 to 1.013. For example, by controlling the temperature and time of the treatment, 'effective heat treatment can be performed in an atmosphere containing H2O. Of course, the above range can be obtained by appropriately adjusting the temperature and time of the heat treatment. When using solid phase In the method, because the ratio of the c_axis / a_axis may decrease with the conditions of decomposition of the synthesized powder, the (CNS) Λ4 lattice (2I0x 297 mm) I.— ^ ---: --.-- install ------ order ------. Line (please read the precautions on the back before * 7 this page) Ministry of Economic Affairs. ¾ Printed by the Property Cooperative Consumer Cooperative 4ί9686 Α7 Β7 The Ministry of Economic Affairs * Standards Bureau ’s work-consumption cooperation Du Yin 11 V. Description of the invention (6) The conditions for solution must be controlled 3 After the above heat treatment, each particle of barium titanate powder shown in Figure 2 and Figure 3 'The ratio of the diameter of the low crystallinity portion 21 (i.e. Rate) is predetermined to be less than 0.65. Such a diameter ratio can be obtained through a heat treatment with a heating rate of 1 .C / min or slower. This provides the average grain size and warp of the barium acid powder. The relationship between the average grain size of the fired dielectric ceramic, that is, the ratio of (average grain size of the calcined ceramic) / (average grain size of the barium titanate powder provided) (expressed as R) is better It is 0.90 to K2. In short, it is best to avoid a considerable degree of grain growth during the sintering of ceramic materials. For example, for this purpose, the heart component and [or] Mg component, Sl-based flux And so on into the titanate button powder. In general, the additives may be incorporated into the barium titanate powder in the form of an oxide or a rimate powder. In other words, you are worried about the state of the art. Barium titanate powder is coated with a solution containing these additives and then tertiary ... This kind of barium titanate powder is produced by scorching. Dielectrics are used for lamination. Tao Hong electronic components, as shown in the picture, are in capacitor 1. As shown in Fig. 1, 'multilayer capacitor 1 includes ~ multilayer 3, each of which has a plurality of multi-layer dielectric layers 2' and a first-external electrode "_ second outer: electrodes 7 are provided separately Layer 3—the first side face and a second side face. This entire tree capacitor is partly composed of a rectangular flat: a chip-type electronic component. In the layer 3, the first-internal electrode 8 and the second electrode Alternately matching the old music and once again applicable to China National Standard Xin (CNS) Λ4 specifications (2! 0X 297 public hair ---- 1 ---: ----- installation ------ order ---- --- Wire (please read the precautions on the back before filling this page) Printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs and printed by the cooperative 419686 A7 _______ B7 V. Description of the invention (7) is the internal conductor 3rd-the internal electrode 8 is It is formed along the specific interface between the dielectric ceramic layers 2 so that one end of each of the internal electrodes 8 is exposed to the side of the laminate 3: above the side 4, so it can be electrically connected to the first external electrode 6, but the first An inner electrode 9 is formed along a specific interface between the dielectric ceramic layers 2 so that each of the inner electrodes 9 is on the second side of the laminate 3, above Therefore, it can be electrically connected to the second external electrode 7, the ceramic ceramic material layer 2 in the ceramic material layer 2 contains the above-mentioned dielectric ceramic 3 in order to manufacture the ceramic material capacitor 1 The initial materials provided include the main ingredients such as cinnamic acid lock, χ, and the additives of the distorter " smteiabiiity " 3 that are also made with box order f-bamboo weighed in a pre-washed bowl and wet The mixed powder is then mixed to form a mixed powder. However, a machine binding agent and a falling agent are added to the mixed powder, so as to support the mud table, and the mud is used to manufacture the ceramic green sheet 3 that forms the dielectric ceramic layer 2. Then, The conductive paste films of the internal warfare electrodes 8 and 9 are formed on this particular ceramic-grown embryo sheet. The conductive paste film contains a rhenium base metal buckle, such as nickel or copper, or an alloy thereof, and passes through a kind of image: Formed by a printed circuit, vapor deposition, or electrical bonding method. A plurality of m blanks 'including those of conductive pastes' which have been formed thereon as described above are laminated, pressed, and cut, if necessary. Therefore, 'Epiphyseal layer 3, its ceramic green sheet and those within The internal electrodes 8 and 9 form a laminate along a specific interface between the ceramic slabs, and one end 8 and 9 of each internal electrode is exposed on the surface 4 or 5. CNS) a4 ^^. (： 1〇χ797 ^ ---: ------.-- install --------- order ------ Λ (Please read the precautions on the back before (Fill in this page) 96 96 Printed by A7 B7, Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention (8) Layer 3 is then calcined in a reducing atmosphere to transform barium titanate powder into dielectric ceramics. In this step, the above-mentioned grain size ratio R is controlled to fall within the range of 0.90 SR magic.2. A first outer electrode 6 and a second outer electrode 7 are formed on the first side 4 and the second side 5 of the laminate 3, respectively, so as to interact with the first inner electrode 8 and the second inner electrode of the calcined laminate 3 The exposed end of 9 is in contact. There is no particular limitation on the composition of the materials for manufacturing the external electrodes 6 and 7. More precisely, the materials used may be the same as the internal electrodes 8 and 9. The external electrode may also be composed of a sintered layer containing conductive metal powder, such as a powder of Ag, Pd, Ag-Pd, Cu or Cu alloy: or a sintered layer containing the above-mentioned conductive metal powder and A mixture of glass-breaking raw materials, such as B2O3-Li2O-Si02-BaO, B203-Si02-Ba0'Li20-Si02-Ba0 or BWrSiOyZnO. The material composition of the external electrodes 6 and 7 is appropriately determined after taking into consideration the factors related to the laminated ceramic trough 1 (such as the use or the use environment). As described above, the external electrodes 6 and 7 can be formed by coating. The metal powder paste on the burnt layer 3 is formed after burning. Those electrodes may also be burned by applying this paste to the unfired buildup 3 at the same time. The external electrodes 6 and 7 can be coated with coating layers 10 and 11, which are formed of Ni, Cu, NbCu alloy, etc., respectively, as needed. Those coating layers 10 and Π may be further coated with a second coating layer 2 and 3, which are respectively composed of solder 'tin. The invention will be described in detail below by way of examples, which should not be construed as limiting the invention. This paper size is applicable to China National Mou (CNS) A4 specification (; M × X 297 mm) ----: --- 1--i--t ------ ΐτ -------涑 (Please read the precautions on the back before filling this page) 11-t # 4 Α7 Β7 Five Inventions (g) Example The multilayer ceramic capacitor manufactured in this example is a multilayer ceramic with the structure shown in Figure 丨 and _ Capacitor. | The barium titanate materials of different compositions shown in Table 1 are prepared by the hydrolysis method. The particle size is between 50 nanometers (nm) and 70 nanometers. And the perovskite structure lattice contains many Cubic structure of OH group. By heat treating these materials under different conditions (such as an atmosphere containing h2o), they have different Γ c / a ″ 値 (c-axis / a-axis ratio), average grain size, maximum grain size, 0 Η The barium titanate powders A to N having a base content and a diameter ratio were prepared. (Treatment during heat treatment is decomposed after heat treatment ------- r --- rI ---- install-i Please read the notes on the back before writing this page) Order _ Ministry of Economy Central Samples of the Bureau of Shellfish Consumer Cooperation Du printed tabulations-BaTlOs (Ba 丨, Ca.). TiO, c / a Almost the average particle size, maximum particle size Η base content 丨 powder. X m (μιϋ) (μιη) (% ) ------ A * 0.00 1.005 1.002 0.07 0.20 1.40 0.8 B 氺 b.oo 1.005 1.005 0.09 0.25 1.20 〇. C 0.00 1.015 1.005 0.13 0.30 0.60 0.4 --D 0.00 1.015 1.007 ": 〇Γ2〇0.40 0.20 0.2 ----- E 0.00 1.015 1,009 0.25 0.45 0.10 F * 0.00 1.015 1.011 0.25 0.50 0.1 〇Ί · ».- 0.1 ^ -person •• ·· G ^ 0.00 1.015 1.009 0.35 0.50 0.1ft ^ 0.1 Ά — H氺 0.00 1.015 1.009 0.25 '〇.Τ〇 0, UT —! 0.05 1.010 1,005 0.30 0.80 0.4 J 氺 0.05 1.010 1.002 0.15 0.30 0.90 0.TK 〇7ϊ〇π 1.015 1.009 0.25 0.45 0.20 αι L 氺 0.10 1.015 1.011 0.25! 0.45 0.10 ; 『0.1 丨 M 氺 0.10 i.010 1.00 to 0.35 0.60 0.10 product 0.1 today” ΝΨ o.to 1.010 1.005 ojlJ 0.30 0.85 warehouse 7 paper The standard is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) -12- Jingdi Bureau of Intellectual Property Finance Bureau: 4 × 96β6 A7 Β7 printed by Yuecong Cooperative Cooperative 5. The description of the invention (1Q) is shown in Table 1 as " The "C / a" value is determined by X-ray diffraction of the titanate pin powder. That is, the result obtained from X-ray diffraction is the use of Rietveld analysis to make X-ray contour fitting for accurate The lattice constant is determined by ground. The average grain size and the largest grain size can be measured by observing the powders with a chinlock under a scanning electron microscope. The barium titanate powder is analyzed by thermogravimetry and measured at 150 ° C or higher weight loss' to measure its OH group content. The diameter ratio shown in Table 1 is the ratio of the diameter of the low crystallinity portion to the particle size of the powder, and is determined by cutting the powder to obtain a thin film test piece which can be observed under a transmission electron microscope. When a powdery film-like test piece is prepared by a cutting process, the 4 degree of powder and the diameter of the low crystallinity portion of the powder may change. Specifically, because the low crystallinity part is not always located in the center of a powder, the size of this part must be changed depending on the cutting position when the film is prepared. Therefore, in order to observe, the size of the selected particles It has a particle size similar to that observed with a scanning electron microscope. The diameter ratio is an average diameter ratio calculated after observing more than 0 such particles. The "BaTi03 powder" in the first column of Table 1 corresponds to powders A to Η 'materials (each of BakCaJmTiOs) χ 11 is 0.000, so powders A to Η do not contain C a' but powders I to ν It contains ca. Their " X " is understood to be 0.05 or 0.10, and the additives added to the barium titanate powder as shown in Table 丨 are also provided in Tables 2 and 3. Additives for the composition. To be more precise, for samples Nos. 1 to 17 shown in Table 2, R e (RE for any G d, D y, -13-f, CNS) Λ4 specification is provided. (2 | 0 ^ _: 297 public welfare, — 1-1-! ---, .--: --- install ------ order ------ line (please read the precautions on the back first) Buy this again) 86 A7 B7 V. Description of the invention (") Ho, and Er), Mg and Mn are added to BaTi03 in the form of one of the samples A to Η. The flux containing si is provided as the main Ingredients. For samples Nos. 18 to 29 in Table 3, Mg and Mη were provided as additives to be added to any of the above samples I to N (Ba ^ CadTiCb. Also included as the main ingredient (S i, T i)-B a 3 Table 2 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs? Private sample BaTi Oj + aRE + βΜ ^ 4-γΜη Si-containing sintered BaTi03 a (Cheng Xu, Mor) β (component, γ (component, binding agent ( Type Gd Dy Ho Er Morr) Morr) Serving, Morr) 1 A 0.02-0.020 0.005 -1 _ > 2 B 0.02 0.020 0.005 2 3 B 0.02 0.020 0.005 4 4 C 0.02 0.020 0.005 5 C 0.02 0.020 0.010 λ j 6 C 0.02 0.015 0.005 Λ 7 C 0.02 0.015 0.005 4 8 C 0.02 0.010 0.020 6 9 D 0.02 0.010 0.005 2 L0 D 0.02 0.020 0.005 * > ο 11 E 0.02 0.010 0.005 Λ 12 E 0.02 0.020 0.005 Λ J 13 E 0.02 0.010 0.005 3 14 E 0.02 0.010 0.005 4 15 F 0.02 0.010 0.005 4 16 G 0.02 0.010 0.005 4 17 Η 0.02 0.010 0.005 4 -14- The paper's scale is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 cm) „r ----- Install-(Please read the precautions on the back before filling out this page)

、 1T line 4 1 ^ 686 A7 B7 V. Description of the invention (12) Table 3 Sample No. (Ba,

BaTi03 (type) 18 19 20 21 22 23 24

K 25

K 26

K 27

L

2S Μ 29 Ν • ^^ 〇Ό05, Ca,) Tj〇3 + P (component, mole) 0.02 0.02 0.02 0.02 0.02 0.02 0,01 0.01 0.0] 0.01 0.01 0.02

Individual additives shown in Tables 2 and 3 of the China Standards Bureau staff of the Ministry of Economic Affairs will be converted into alkoxide compounds that are soluble in organic solvents and then added to the organic compounds that have been dispersed in organic solvents. In the powder of barium titanate. More specifically, for samples Nos. 17 to 17, the individual additives added to the barium titanate powder form "BaTi03 + aRE + pMg + 7Mn" as shown in Table 2, whose "quot" ct " β 'I,', " and " Si-containing fluxes " are all moles at each cost: > For samples Nos. 8 to 29, the individual additives added to the barium titanate powder are all In terms of the number of moles, p " 15-This paper size is in accordance with the Chinese National Standard (CXS) Λ4 specification (210X 297 g t) ------ L ---- batch clothes ------ 、 玎 ------. A (Please read the precautions on the back before filling this page) Α7 4 ^ 686 __________ Β7 V. Description of the invention (坳, γ, and "flux containing (Si, Ti) -Ba") It is shown in Table 3 as (Ba) _xCax) Ti03 + βΜ ^ + γ ^ / Γη ”a In order to dissolve the above additives in organic solvents, they can be converted into alkoxy groups as described above, or It is converted into acetylacetonates or metal soap. The resulting slurry is removed by evaporation and drying with an organic solvent and further heat treatment to remove it. Next, for each barium titanate powder sample to which additives have been added, a polyvinyl butyral binding agent and an organic solvent (such as ethanol) are added, and those ingredients are wet-milled A ceramic slurry is prepared. The generated slurry is molded into a sheet shape with a scalpel || Γ This obtains a rectangular green embryo sheet with a thickness of 15 microns. Then, on the generated ceramic green sheet, The conductive paste containing N 丨 as the main component is used to form the conductive paste film of the internal electrode by printing. Next, a plurality of ceramic green embryo sheets obtained in this way are laminated to the conductive paste film on the sheet. The front ends are alternately arranged so as to obtain a build-up layer 3. The build-up layer is heated in a nitrogen atmosphere at 350 ° C to burn out the bound rhenium, and then in a N2-H2O reducing atmosphere at 10-9 to 10-! 21 Oxygen content of ^ 3 was sintered at the temperature shown in Table 4 for 2 hours. For the opposite side of the sintered laminate, a silver paste containing B2O3_Li20-Si〇2-BaO glass material was added, followed by 600 Combustion in a nitrogen atmosphere to obtain external power connected to the internal electrode = > The external dimensions of the produced multilayer ceramic capacitors are 5.0 mm wide, 5.7 mm long, and 2.4 mm thick, and the dielectric ceramic layer between the internal electrodes is -16- This paper size applies to Chinese national standards CN (CN: S) A ·! Specifications (210X2W mm) I -------.-- Installation ------ Order · ------.,!: (Please read the back first Please pay attention to this page, please fill in this page) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 j ^ 6e 6 Α7 Β7 5. Printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by the male workers and cooperatives of the Fifth Cooperative Association, and the thickness of the invention is [micrometer]. The total number of effective dielectric ceramic layers is 5, and the area of each opposite electrode is 16.3 X 10-6 square meters. The electrical properties of the known samples were measured in the following manner. The electrostatic capacitance (C) and dielectric loss (tans) are measured using an automatic bridge instrument according to Japanese Industrial Standard 5102, and the dielectric constant (ε) is determined by the generated electrostatic capacitance. In order to measure the insulation resistance (R), an insulation tester was used: an additional 10 volts (V) DC was applied for two minutes to obtain an insulation resistance (R) of 25 X, and the resistivity was calculated. Regarding the rate of change of the electrostatic capacitance with respect to temperature, it shows the rate of change of the static capacitance (W / C 2〇) 'in the range of -2 5 ° C to + 85' C, and -55 Range of ° C to +125 ° C relative to the static capacitance change rate at 25 ° C (△ c / c25) ° In the high temperature load test, when the insulation resistance of 10 watts plus 10 volts is applied at 150 ° C Process variation is measured = In this test, the average life of the sample is evaluated, where the life of the sample is the equivalent time that is determined when the insulation resistance (R) of each sample falls to 105 Ω collapse. The breakdown voltage is measured at a boosting rate of 1000V / 中 plus a DC voltage to measure the average crystal grain size of the dielectric ceramics contained in the generated multilayer ceramic capacitors. 'The surface is observed under an A-type electron microscope, and the average particle size obtained by using the starting material used in Table 丨 is not measured. The ratio R is measured, which is also the average grain size of the dielectric ceramic. / (Average grain size of the initial raw material). The results are shown in Table 4. s The paper size is in accordance with the Chinese National Standards (CNS) λ4 specification (2ίΟΧ) 97 public) -----.----- ^ ------, 1T-- ---- '" (Please note the matters on the back of Ktii before filling out this page) 17- 8β ΑΊ Β7 V. Description of the invention (15) Member of the Central Bureau of Standards of the Ministry of Economic Affairs, second cooperation, f. Du printed Table 4 Sample Poor 丨1 Dimensional ratio of temperature 窀 窀 芜 靴 Boot pull 1 shirt material change rate, electricity rental rate, i collapse almost average loss iC / Ct α + 85Έ iC / Cii H2S0 1〇0ί Xuanzang life 'j ⑻ (W- (%) (w (%) (0 · αη) (kV / tnn) (h) 1 μm 1100 1.30 1300 L8 —5.0 -12.6 -30.7 13.1 7 6 9 6 2 Π00 1.05 1530 2.3 -8.0- 10.5 -18 * 9 13.1 8 4 2 5 3 * 11G0 1.55 HT0 2.1 -24.6 -5.6 -40.8 12.9 8 8 5 4 4 Umbrella UC0 0.80 1160 2.7 —6.5 -11.6 -20.5 13.1 7 8 8 6 5 1150 1.05 1680 1Λ — 9.0 -7.5 -1Z6 13.1 8 8 9 3 6 1150 1.10 1750 2 * 3 -B.8-7-6 -11.5 13.1 8 4 9 0 7 1150 1.18 1720 2.4 --10.2 ~ T.5 -1Z4 13.1 8 6 9 2 8 * 1150 1.40 1260 2.5 --Z1- 4-丄 8,4 -35.2 13.2 T 4 4 6 9 * 11CO 0.T5 1160 1.1 -6.0 -9.6 -28.4 13.2 7 4 1 0 5 10 1150 U0 1850 Z4 -10.0 -E.8 -13.7 13.2 8 5 8 5 11 * 1125 0.80 1160 2.3 -11.0 -9.2 -24.6 13.2 5 9 6 12 1200 1.05 2020 Z5 -11.3 -8.5 —13_ 6 112 8 8 9 1 13 1150 1.10 1850 Z5 — 11.5 -8.2 -13.5 13.1 5 9 3 U wood 1300 1.35 2360 3.4 —26, 6 —3. -25-2 12.9 4 4 3 3 15 * 1175 1.05 2H0 Μ ™ 11.3 -8.2 ~ 12,4 13.2 8 5 1 6 16 ^ Π75 1.10 2250 15 -13.5 -8.9 -13.7 13.2 8 8 2 5 Π * | 1150 1.05 20 00 ZZ4 — 11.4 -12.6 H9.T 13.2 1 fly 12 18 * 1100 0.T5 870 U-8.0 -8.8 -28.7 13,2 7 5 10 5 '19 Π30 1.00 1670 1Λ -10.0 -5.5 -13.4 13.1 9 1 8 4 20 1100 1.15 1540 2.5 -8.0-4' 5 -11.6 13.2 8 6 7 8 21 * 1130 1.25 1220 2.3 —1 6 6 6 67.8 12.8 8 2 3 Z2 * 1100 1.05 1120 Z4 -9.0 — 1.4 -30.8 13.1 4 4 5 5 23 * 1100 1.25 U80 3.6 --25 * 5 3.6 36. T 13 7 5 18 24 * 1150 0.70 1060 8.T -T.0 —8 · 5 -28.5 13.2 9 6 8 8 25 Π50 U0 2160 2.5 — 15.5 —4_ 2 10.3 13.1 8 8 8 4 26 1150 U8 2340 2 * 5 -21.2 —4.5 13.5 13.2 8 Τ 8 3 2U 1250 1.05 2060 3.4 -15.0 -2.3 25.5 1 6 1 5 16 m 1200 1.05 2150 2.8 -17.0 -3 · 3 21.6 12.8 7 5 1 B 29 * 1100 1.10 1360 Zi, -7.5-6 · -14.T 13 8 8 9 0 (Read the first note on the back Please fill in the clothing page for further details) -18-This paper size is applicable to Chinese National Standards (C, TS) Α4 specifications (2 丨 0 x_ 297 Gongchu)-Equipment · --- —Order ------ Travel A7 B7 l96ee V. Description of the invention (π) The dielectric M of the present invention is characterized in that by using a counter-rotating structure (whose ratio of the b-axis / a-axis is in the range of 103 to 1010) , And the content of 0H groups in the crystal lattice is not higher than 〇wt%) and obtained by sintering ^ It is preferable that the maximum particle size of the barium titanate powder as the initial raw material is not more than 0.05 micron 'and its average particle size It is between 0 "and 0.3 microns. It is known that the above-mentioned particles each include a low crystallinity portion and a high crystallinity fraction, and the diameter of the low crystallinity portion is 65 times or more than that of the particle powder, and (average dielectric The ratio of the size of the ceramic material is large) / (average particle size of barium titanate powder) is 0.90 to 2 .2, so that a considerable amount of grain growth does not occur when the ceramic is sintered. In Table 4, therefore, the sample numbers marked with * and the powder marked with * in Table 1 do not fall outside the above-mentioned preferred range or the scope of the present invention. 3 First, by using A to Samples 1 to 7 in Table 4 obtained from one of the H raw materials were analyzed by transmission electron microscopy. The sentence shows that the burned ceramics are similar. Sentence: The grain boundaries are like 'G d, ID y, Η 〇, or Er or other rare earth elements (RE) diffuse and form a shell part, and in the center of the ceramic grains form a core part; that is, in each grain, the fired ceramic in each grain Establish a core-shell structure, in which the core and the shell have different compositions and crystal systems3 As can be seen in sample No. 丨 in Table 4, the ratio of the ^ axis / 3_ axis in the perovskite structure is less than 1.003. (As shown in the table! The powder material A) Long Buqi i 'Because an additive has an excessively high reactivity, it unfavorably causes the sintered ceramics to grow grains and increase the change in temperature-dielectric constant characteristics. As the data of sample No. 5 in Table 4 clearly show, the use of c_axis / a--19- this paper music standard is applicable to the middle-country ^ car (CNS) Λ4 specification (: 10 × mm ~ ~ ---------- Equipment ------ Order ------ Λ (please read the notes on the back before filling in the wooden pages), the staff of the Central Standards Bureau of the Ministry of Economic Affairs, consumer cooperation. Printed by the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China. * Table 4 19686 V. Description of the invention (17) Powder materials with an axis ratio greater than 1.010 are not suitable, as shown in Table 丄, powder material F, because it is related to The poor reactivity of the additive shortens the average life. In addition, when the dielectric ceramic layer is thinned as in this example, its reliability is poorly deteriorated. Even if the c-sleeve / a-axis ratio of the powder material is Between 〖〇03 and 1.01 〇, and its OH group content is less than 1.0 weight. / 〇 .. The data of sample No. 16 in Table 4 shows that 'if the average particle size of the powder used is greater than 0.3 microns, As with the powder material G in Table 1, its average life will be relatively shortened. In addition, when the dielectric ceramic layer is thinned as in this example, it is reliable. Deteriorating a badly similar situation 'Even in the case where the c-axis / a-axis ratio and its low hydrazine content are in the above-mentioned range of the invention, the data of sample No. 17 in Table 4 It is clearly stated that if the average particle size of the powder used is greater than 0.05 micrometers, as in the powder material of Table 丨, its average life will be relatively shortened. In addition, when the dielectric ceramic layer is as thin as this example , The reliability deteriorates poorly. Even in the case of the powder materials C, D, and E in Table 1, the c-axis / a-axis ratio of the powder material is between 1.03 and 1.01. Its η-group content is less than 1.0% by weight, its maximum particle size is less than or equal to 0.5 microns, and its average particle size is between 0.1 and 0_3 microns, as shown in Table 4 for samples 4 ′ 9 and 1 1 (whose R 値 is less than 0.90) or samples 8 and 14 (whose R 値 exceeds 1.2) are clearly visible, and the dielectric constant will increase with temperature.

In contrast, although the dielectric ceramic layer thickness was as thin as 1 micron after Tables 5, 6, 7, 10, 12, and 13 in Table 4, the rate of change in electrostatic capacitance with temperature met Japanese industrial specifications B -20 specified in the range of -25 ° C to +85 X: This paper is restored to the standard of China National Standard (CN-S) A4 (210X297 male dragon (please read the precautions on the back first and then write the book in trivial form) Education). Packing and ordering A7 B7 4l9eee V. Description of the invention (18) Characteristics and meeting EIA specifications. Furthermore, in the high temperature load test, these samples lasted 70 hours or even longer until collapse occurred. ^ 4 朋$ Reward, and can be burned at 1200. (: or lower temperature = static at the applied DC voltage * A change in the %% of valleys is not greater than 5% and therefore can ensure a high voltage rating 3 The transmission electron microscope analysis of the sintered samples Nos. 8 to M shown in Table 4 was obtained using the powder material shown in Table 丨. It can be determined that it is the same as the samples Nos. 1 to 7 The homogeneity and heterogeneous crystal system of the related individual ceramic grains have not been observed here. In the perovskite structure, when the c_axis / & _axis ratio 値 is lower than 1003, the powder material is like the powder material family in Table 丨, which is as clear as the data of samples U and 23 in Table 4. It can be seen that the temperature characteristic of the dielectric constant will increase, so that the occurrence of the increase has nothing to do with the degree of grain growth during the sintering. For example, if you compare R 2 of No. 2 No. 2 and No. 3 of Sample No. 2, you can understand s as shown in Table 4. Sample No. 2-7 clearly shows that using a perovskite structure with an axis / a-axis ratio higher than 1010 (such as the powdered material shown in Table 丨 L) is inappropriate because of its unsatisfactory temperature. — Dielectric constant characteristics, • Short rain life and poor reliability. Even for powder materials in the table [in the example with κ, the fineness of the powder material's a-axis ratio is 1.003 to 1.0. 〇, its OH group content is less than 0% by weight, its maximum particle size is less than or equal to 0.05 microns, and its average particle size is between 0, 丨 and 0.3 microns, the samples in Table 4 S and 2 4 (the R 値 is less than 0.90) Bite sample No. 2 (whose R 其 is more than 12) can clearly indicate that if the planting of r is less than 0.90 or less than 12, the dielectric Depends on the number will increase. -21-Applicable to China National Standard (CNS) Λ4 specification (210X29 · / mm) as far as the paper size is concerned ------: --.-- ^ ------ J1T ------, Α (Please read the notes on the back first and fill out this page) The Central Bureau of Standards of the Ministry of Economic Affairs has negative cooperation with X and f. The company printed 4 ^ 68 6 A7 B7. Sample five, the description of the invention (1 bow i.ou), the cm base axis ratio is ^ 003 = No. According to the description, if the powder used has an average particle size greater than 03 microns and its larger particle size is greater than 0-5 microns As shown in the table, the temperature-dielectric constant characteristics of 'J —' cannot be made, the length of 1M is not shortened, and when the dielectric layer is changed, the lifetime will be degraded badly. . As can be clearly seen in Sample No. 29 in Table 4, when the powder material N shown in Table 1 is used in this example, each of the acid-locking powders μ j. Bu Bu contains—low crystallinity. (The diameter is less than 65 times of the particle size of the powder), and its temperature-dielectric constant characteristics will be deteriorated. Conversely, referring to the samples of No. 9, 20, 25, and μ in Table 4, although the thickness of the ceramic layer is as thin as 1 micron, the rate of change in capacitance with temperature meets Japanese industrial specifications. _25 ° C to +85 ° C B characteristics 'and meet the EIA specification -5 5 X: to +125 3C range t7R characteristics 3 again' in the high temperature load test, these samples Durable for 70 hours or longer until a crash occurs, and can be burned at 1 200 ° C or lower ^ Its static capacitance does not change much with the applied DC voltage, and it can ensure high voltage rating . As mentioned above, even if each grain of a dielectric has a homogeneous composition and a uniform crystal system, that is, even if those grains do not have a core, a shell structure, and control of grain growth when sintered, Manufacture of dielectric ceramics with excellent temperature-dielectric constant characteristics and high reliability, such as the examples in samples Nos. 19, 20, 25, and 26. The above example points out a multilayer ceramic capacitor in the form of a multilayer ceramic capacitor -22-) Λ4 Specification (: Does it look like a common man) ---.-- install ------ tr ------ Λ ( Please read the notes on the back before filling in this page) Printed by Male Worker Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs 11 4 ΐ9〇86 彡 J 9 6 8, A7 -----__ B7 V. Description of Invention (2〇) 1 I ~ Free electronic components; however, in other laminated electronic components (such as multi-substrates made with almost the same method), it has been confirmed that the same results can be obtained. As described heretofore, in the dielectric ceramic of the present invention, 'by controlling the c_axis / a_axis ratio in the perovskite structure and the 0H group content in the crystal lattice', it is preferably- The control of the maximum particle size, average particle size, powder particle structure based on crystallinity, and grain growth of barium titanate powder used as an initial material during calcination, etc., achieves an excellent temperature-dielectric constant characteristic And improved reliability. Therefore, by using the dielectric ceramic of the present invention, a high-performance% -layer ceramic electronic component can be obtained, which has excellent temperature-dielectric constant characteristics and high reliability. 3 To be precise, when a dielectric ceramic is used When a multilayer ceramic electronic component (such as a multilayer ceramic capacitor) including a dielectric ceramic layer and an internal electrode stacked on top of each other, even at a thin ceramic layer having a thickness of not more than 1 micron, the temperature is The characteristics of the electric constant can be stabilized, and JL is therefore advantageous in miniaturizing and thinning multilayer ceramic electronic components. When a dielectric ceramic is produced in a reductive atmosphere, the ceramics will not be reduced during sintering. 3 Therefore, the invention uses laminated ceramic electronic components made of dielectric ceramics, such as nickel or nickel alloys. The base metal is used as the material of the internal conductor to reduce the cost of multilayer ceramic electronic components such as multilayer ceramic capacitors. 3 The dielectric ceramic according to the present invention provides excellent temperature-dielectric constant characteristics and excellent reliability. _Whether it has a core " 一 外 'ίί structure-therefore, when a dielectric ceramic does not have a core ~ shell structure, its temperature characteristics-23-) Λ4ίΐ ^ (21〇;' (Please read the note on the back first Please fill in this page for further information.) Installation, 1T Consumer Consumption Cooperation of the China Standard Procurement Bureau of the Ministry of Economic Affairs, printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Printed by the Employee Consumption Cooperative of the Central Standardization Bureau 4 49686 v A7 B7 V. Invention Description (21) and Reliability It is not affected by the dispersion state of an additive component, and thus reduces the change in characteristics with the sintering conditions. -24- (Please read the precautions on the back before filling this page)

^^^^ 1 Γ--H-_ 1 · 1 1 I ^^ 1 * I --- I — Ί ·-I This paper size is applicable to the Chinese national labeling CNS) Λ4 is present ()

Claims (1)

—14 19686 The 88100659% patent application _ plead for the final original version of the patent application ^ Six, the scope of patent application AS BS C8 D8 2. 4. 6. Central China Fengfeng Bureau, Ministry of Economic Affairs, shellfish consumer cooperation Du Yin *. 8. — A dielectric ceramic obtained by calcining barium titanate powder, the titanic acid <, the non-converted ore-converted ore structure in the axis-to-draw ratio is in the range of 丨 to 1′〇1〇 And the content of the 0H group in the crystal lattice is 0 wt% or less. For example, the dielectric ceramic of item I of the target garden of patent application, wherein the maximum particle size of the barium titanate powder is not greater than 0.5 micrometers, and the average particle size thereof is 01 to 0 3 micrometers. The individual particles of the barium titanate powder include a low crystallinity portion and a high crystallinity portion, and the diameter of the low crystallinity portion is less than 0.65 times the particle size of the powder. For example, the dielectric ceramics in the scope of patent application No. 1 are defined as (dielectric ceramics: average grain size) / (average particle size of the barium titanate powder provided). The ratio R is between 0.90 and 1. , 2 in. For example, for the dielectric ceramics under the scope of patent application, the grains constituting the dielectric ceramics have a core-shell structure, and the composition and crystal system between the core and the shell are different. A dielectric ceramic, in which the crystal grains in the dielectric ceramic have a homogeneous structure with a uniform composition and a crystal system. A method for manufacturing a dielectric ceramic, which includes the step of providing a barium titanate powder, 'the c_ — / a-axis ratio 疋 in the perovskite structure of this barium titanate powder is in the range of 1.003 to 1.010, and its crystal The content of QH group in the grid is not higher than 1.0% by weight; and the step 3 of calcining the barium acetic acid powder is the method for manufacturing a dielectric ceramic according to item 7 of the patent application, wherein the step of providing a barium titanate powder In the paper, a barium titanate powder is provided. The paper size is in accordance with China National Standards (CNS) from the specifications (210 X 297 mm (please read "Note on the back side before filling this page)." The Department of Industrial and Consumer Cooperatives of the Ministry of Supervision of the Ministry of Finance and Economics is a member of the Industrial and Consumer Cooperative Association. Ft / !!! 8e g __________ D8 6. The maximum particle size of the patent application park is not more than 0-5 microns, and the average particle size is between ol and 0.3. 9 'The method for manufacturing a dielectric ceramic according to item 7 of the patent application scope, wherein in the step of providing a barium cinnamate powder, the individual barium titanate powder particles include a low crystallinity portion and a high crystallinity portion, and The diameter of the low crystallinity part is lower than that of the powder particles 0 65 times. 10 'If the method of manufacturing dielectric ceramics according to item 7 of the patent scope, in the stepped snails fed in,' is defined as (average grain size of the dielectric ceramics after calcination V (provided The ratio R of the barium acid powder average particle size) is controlled to fall within the range of 0.90 to 1.2 β 1 1. The method for manufacturing a dielectric ceramic according to item 7 of the patent application, wherein the crystal grains of the dielectric ceramic are formed It has a core-shell structure after firing, and its composition and crystal system are different between the core and the shell. 12. The method for manufacturing a dielectric ceramic according to item 7 of the patent application 'wherein the grains in the dielectric ceramic are in After sintering, it has a homogeneous structure with a uniform composition and crystal system. 13. A laminated ceramic electronic component, comprising a laminated layer, which is specified by a plurality of dielectric ceramic layers and one of two adjacent dielectric ceramic layers. Formed by an internal conductor formed by an interface, wherein the dielectric ceramic layer includes a dielectric ceramic material obtained by burning saccharic acid powder, and the c-axis / a-axis ratio in the dance structure is .003 to .010, and its crystal The content of 0% in the grid is not more than 1.0% by weight. 14. If the laminated ceramic electronic component of item 3 of the patent application, the maximum particle size of the acetic acid pin powder is not more than 0.5 microns and its The average particle size is in -----.-- r--install ------ order ------ line < Please read the precautions on the back before writing this page) 4, 9 & ee A8 B8 C8 D8 Printed by the Consumers' Cooperative of the Central Bureau of the Ministry of Economic Affairs of the Central Bureau of Li Bureau «. The scope of patent application is between 0, 1 and 0 · 3 micrometers a. It makes the individual acid particles contain-a low crystallinity portion and a-high crystallinity portion, and the diameter of the low crystallinity portion is 0-65 times smaller than that of the powder. For example, the laminated Tao Ai electronic component of the 13th patent scope, which is defined as the ratio of (the average grain size of the dielectric ceramics) / (the average grain size of the acid-locked powder) is 0'9. Fan Guzhong a to 1.2 is the multilayer ceramic electronic component as described in the patent application No. π, in which the grains constituting the dielectric ceramic have a core-shell structure, and the composition and crystal system between the core and the shell are different. For example, the laminated ceramic materials of the 13th scope of the patent application, where the crystal grains in the dielectric ceramic materials have a homogeneous composition and a homogeneous structure of the crystal system "19, such as the laminated ceramics of the 13th scope of patent application An electronic component, wherein the inner conductor comprises a base metal ^ 20. For example, the laminated ceramic electronic component according to item 19 of the patent application scope, so that the inner conductor contains a medium or a nickel alloy. 21_ The multilayer ceramic electronic component according to item 13 of the patent application scope, further comprising a plurality of external electrodes arranged at different positions on one side of the multilayer, wherein a plurality of internal conductive systems are arranged so that each One end of the conductor is exposed on the side for electrical contact with an external electrode. 22. —A method for manufacturing a multilayer ceramic electronic component, which includes providing a standard of titanium 3—3 good paper, 8¾ standard (CNS> A4 wash grid (210X29 * 7mm) -------- -! — Equipment ------ ir line-1 Please read the notes on the back of TS first * fill in the poverty] ^ 196 ___ ^ 196 ___ Order from the Ministry of Economic Affairs to lead the bureau to cooperate with the shellfish consumer cooperation seal ft A8 B8 6. Apply for a patent application step of barium acid powder. The c-axis / a • axis ratio in the perovskite structure of this barium titanate powder is in the range of 1.003 to 1.010, and the content of 01 | More than 1.0% by weight: a step of making a laminate, wherein a plurality of ceramic green sheet material comprises the barium titanate powder and an internal electrode so that the internal electrode exists along a specific interface of the ceramic green sheet material; and calcining the A step of providing barium titanate powder to provide a dielectric ceramic. 2 3 _ A method for manufacturing a laminated ceramic electronic component such as the patent application No. 22 of the patent application, wherein in the step of providing barium titanate powder, the barium titanate is provided. The maximum degree of powder is not more than 0.5 microns and its average particle size is between 0.1 and 0.3 microns. 2 4. The method for manufacturing a laminated ceramic electronic component according to item 22 of the scope of patent application, wherein in the snail provided with barium acetate powder, the individual particles of the “barium acid powder” include a low crystallinity portion and a high crystallinity 25. For example, the method for manufacturing a laminated ceramic electronic component in the scope of application for patent No. 22, wherein the calcination step is defined as The ratio R of the average grain size of the electrical ceramics) / (average particle size of the barium titanate powder provided) is controlled to fall within the range of 0.90 to 1.2. 26. Manufacturing of laminated ceramic electronic components such as the 22nd item in the scope of patent application Method 'in which the grains constituting the dielectric ceramic have a core and a shell structure after sintering', the composition and crystal system of the core and the shell are different a 2 7. Such as the multilayer ceramic electronics of the 22nd patent application Element manufacturing method 'wherein the crystal grains in the dielectric ceramic have a homogeneous structure with a uniform composition and crystal system after calcination. This paper size is applicable to Chinese national standards (CNS > A4 (2 丨 0X297mm) --------.-- ^ ------- ΐτ ------ lacquer '(please read the precautions on the back before filling in this) ί ) 4,968e SJ C8 ---- — __D8 6. Scope of Patent Application 'One-For example, the method of manufacturing a laminated ceramic electronic component for patent application No. 22, wherein the internal conductor includes a base metal. Μ. 如Apply for a patent ㈣Production method for product of item 28 of love electronic component 'wherein the internal conductor contains nickel or nickel alloy. 30, such as the method of making multilayer ceramic materials for element production of item 22 of the patent scope'wherein the manufacture -The step of lamination includes the following steps: setting the internal electrode along a specific interface between two moth pottery germs, so that one end of each internal conductor is exposed from the side of the lamination-the side of the lamination A plurality of external electrodes are formed so that the exposed end of each internal conductor is electrically connected to the corresponding external electrical connection a 1 I Is I: --- 1 0--J -n- l ^ n -I-(please first "Read the notes on the back and fill in this I again" Order I Printed by the Central Bureau of Work, Ministry of Economic Affairs, Consumer Cooperatives «. 5-